US20140314655A1 - Corrosion and fouling reduction in hydrochlorosilane production - Google Patents

Corrosion and fouling reduction in hydrochlorosilane production Download PDF

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Publication number
US20140314655A1
US20140314655A1 US14/243,822 US201414243822A US2014314655A1 US 20140314655 A1 US20140314655 A1 US 20140314655A1 US 201414243822 A US201414243822 A US 201414243822A US 2014314655 A1 US2014314655 A1 US 2014314655A1
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silicon tetrachloride
hydrogen
superheater
process stream
iron
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US14/243,822
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English (en)
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Stein Julsrud
Anja Olafsen Sjastad
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Rec Silicon Inc
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Rec Silicon Inc
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Assigned to REC SILICON INC reassignment REC SILICON INC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: JULSRUD, STEIN, SJASTAD, ANJA OLAFSEN
Publication of US20140314655A1 publication Critical patent/US20140314655A1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/08—Compounds containing halogen
    • C01B33/107—Halogenated silanes
    • C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage

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  • This disclosure concerns a method for reducing corrosion and/or fouling in hydrohalosilane production plants.
  • a hydrohalosilane production plant includes components such as vessels (e.g., a silicon tetrahalide superheater and a hydrogenation reactor) and conduits for transporting liquid and/or vapor streams to and from the vessels.
  • One or more production plant components may include iron.
  • silicon feedstock may include a trace amount of iron.
  • Iron silicide fouling and corrosion in the hydrohalosilane production plant is reduced by including a sufficient concentration of hydrogen in a silicon tetrahalide process stream to inhibit iron halide formation and reduce superheater corrosion, iron silicide and/or iron phosphide fouling of production plant components (e.g., the hydrogenation reactor), or a combination thereof.
  • the production plant is a hydrochlorosilane production plant
  • the method includes adding hydrogen to a vaporized silicon tetrachloride process stream upstream of a silicon tetrachloride (STC) superheater to form a combined hydrogen/silicon tetrachloride feed having a concentration of hydrogen sufficient to inhibit FeCl 2 vapor formation in the STC superheater, thereby reducing iron silicide and/or iron phosphide fouling, superheater corrosion, or a combination thereof, and flowing the combined H 2 /STC feed into the silicon tetrachloride superheater.
  • STC silicon tetrachloride
  • the combined H 2 /STC feed has a hydrogen mole fraction of at least 0.4, such as a hydrogen mole fraction from 0.4 to 0.9.
  • hydrogen is added to the vaporized silicon tetrachloride process stream in an amount sufficient to produce a H 2 /SiCl 4 mole ratio of at least 0.67:1, such as from 0.67:1 to 5:1, in the combined H 2 /STC feed.
  • the method may further include adding trichlorosilane (TCS) to the silicon tetrachloride process stream before flowing the combined H 2 /STC feed into the STC superheater.
  • TCS may be added to the combined H 2 /STC feed to provide a TCS concentration of 0.05 mol % to 2 mol %, such as from 0.5 mol % to 1.5 mol %.
  • the hydrogen mole fraction may be 0.05 or greater.
  • FIG. 1 is a schematic flow diagram of a hydrochlorosilane production plant.
  • FIG. 2 is a graph of HCl partial pressure versus H 2 mole fraction illustrating the FeCl 2 -FeSi transition as the H 2 /SiCl 4 ratio, HCl partial pressure, and trichlorosilane content vary.
  • Silicon tetrahalides are hydrogenated to produce hydrohalosilanes and silanes. See, e.g., U.S. Pat. No. 4,676,967 and International Publication No. WO 2006/098722.
  • a hydrohalosilane production plant comprises components including vessels, such as a silicon tetrahalide superheater and a hydrogenation reactor, and conduits for transporting liquid and/or vapor streams to and from the vessels. Alloys used in the construction of the production plant components typically are iron-based. Iron also may be present as a trace element (e.g., less than 1% (w/w), or less than 0.1% (w/w)) in silicon feedstock used in the production plant.
  • the temperature in a silicon tetrahalide superheater is sufficient to produce significant vapor pressures of iron halides when the activity of halides is high.
  • significant iron (II) chloride vapor pressures are produced at typical operating temperatures.
  • a hydrochlorosilane production plant 10 comprises a silicon tetrachloride (STC) superheater 20 and a hydrogenation reactor 30 .
  • STC silicon tetrachloride
  • a silicon tetrachloride process stream 40 is pure or includes any HCl, FeCl 2 vapor is produced when iron in the superheater walls reacts with chloride ions. Iron also may be present in the STC process stream 40 when STC is made from silicon feedstock including a trace amount of iron.
  • the STC process stream 40 further may include trace amounts of hydrogen.
  • STC reacts with hydrogen to produce trichlorosilane and hydrogen chloride.
  • Hydrogen chloride can react with iron present in the STC feed and/or in iron alloys within the superheater 20 to produce iron (II) chloride.
  • iron (II) chloride reacts with STC and hydrogen to produce iron silicide.
  • Iron silicide deposits in the superheater 20 and can form a passivating later on the superheater walls, thereby suppressing subsequent iron (II) chloride formation over time.
  • the FeCl 2 vapor may be transported with the superheated process stream 44 to a distributor plate area in a hydrogenation reactor 30 where iron silicides and/or phosphides (if phosphine or other phosphorus-based compounds are present in the process stream) can form in the hydrogenation reactor 30 .
  • Iron silicides and/or phosphides if phosphine or other phosphorus-based compounds are present in the process stream
  • Formation of FeCl 2 vapor also causes corrosion of the superheater 20 .
  • high chloride activities may lead to transport of other alloy elements besides iron. Over the long term, such materials transport and the resulting fouling and/or corrosion may reduce the lifetime of the silicon tetrachloride superheater 20 and/or the hydrogenation reactor 30 .
  • Fouling and/or corrosion are inhibited or prevented by minimizing the formation of iron (II) chloride.
  • Combining hydrogen with the STC process stream drives the equilibrium in equation (3) to the right, thereby favoring FeSi formation and minimizing or preventing FeCl 2 formation.
  • hydrogen 50 is added to the STC process stream 40 before entering the silicon tetrachloride superheater 20 .
  • the combined H 2 /STC feed 42 then flows into the superheater 20 .
  • the STC process stream 40 may be heated to vaporize STC before introducing hydrogen so that hydrogen 50 is added to a vaporized STC process stream 40 upstream of the silicon tetrachloride superheater 20 .
  • Any suitable heater 60 such as a heat exchanger (e.g., a shell-and-tube heat exchanger), can be used to vaporize the STC process stream 40 .
  • hydrogen 50 is introduced at a temperature less than or equal to the STC vapor temperature.
  • the combined H 2 /STC feed 42 may flow through another heat exchanger (not shown) to increase the combined feed temperature prior to entering the superheater 20 .
  • FIG. 2 is a graph illustrating the relationship between FeCl 2 and FeSi during the reaction shown in equation (3), with regard to the H 2 /SiCl 4 ratio, HCl content, and TCS content of the process stream.
  • the data in FIG. 2 was obtained at a total pressure of 30 bar, and a temperature of 823K.
  • curve A indicates the division between FeCl 2 and FeSi phases within the superheater. At a given H 2 fraction, if the HCl partial pressure is above curve A, FeCl 2 predominates. If the HCl partial pressure is below curve A, FeSi predominates.
  • Curve B represents the partial pressure of HCl in a STC/H 2 mixture as a function of the H 2 fraction. For example, when the H 2 fraction is 0.1, the partial pressure of HCl is ⁇ 0.3; when the H 2 fraction is 0.7, the partial pressure of HCl is ⁇ 0.45. Fouling and/or corrosion are reduced or eliminated by maintaining reaction conditions such that the HCl partial pressure curve (e.g., curve B) is below curve A. Under conditions where the HCl partial pressure curve is below curve A, there is less HCl available to react with iron in the superheater alloys (equation (2)), and the equilibrium in equation (3) also is shifted to the right, favoring FeSi formation over FeCl 2 formation. As shown in FIG.
  • Desirable operating conditions are conditions under which corrosion and/or fouling is inhibited by at least 50%, at least 70%, at least 90%, at least 95%, at least 98%, 50-100%, 50-98%, 50-95%, 50-90%, 50-70%, 70-100%, 70-98%, 70-95%, 70-90%, 90-100%, 90-98%, or 90-95% compared to operating under conditions that favor FeCl 2 formation.
  • a combined H 2 /STC feed has a hydrogen mole fraction of at least 0.4, particularly at a hydrogen mole fraction from 0.4 to 0.9, or from 0.4 to 0.65.
  • the hydrogen mole fraction is 0.5.
  • hydrogen may be combined with STC at a H 2 :SiCl 4 mole ratio of at least 0.67:1, such as a mole ratio of from 0.67:1 to 5:1, from 0.67:1 to 3:1, from 0.67:1 to 2:1, from 1:1 to 2:1, or a mole ratio from 1:1 to 1.8:1.
  • the H 2 :SiCl 4 mole ratio is 1:1.
  • Hydrogen stream 50 may be the primary or sole source of hydrogen for the hydrogenation reaction. In some arrangements, hydrogen stream 50 provides only a portion of the hydrogen for the hydrogenation reaction, and additional hydrogen 55 may be provided directly to the hydrogenation reactor 30 . If additional hydrogen 55 is provided, the hydrogen is preheated to a temperature substantially similar to superheated process stream 44 .
  • TCS Trichlorosilane
  • STC process stream also can be added to the STC process stream.
  • TCS reduces the activity of the chlorides while increasing the activity of silicides in the STC superheater (and other places in the process stream), thereby reducing or preventing fouling.
  • TCS in the STC process stream reacts with HCl and reduces the HCl partial pressure.
  • Reduction of HCl in turn reduces the extent of the reaction in equation (2) and shifts the equilibrium in equation (3) to the right, thereby reducing the amount of FeCl 2 produced or even preventing FeCl 2 formation.
  • TCS lowers the HCl partial pressure as TCS reacts with HCl (equation (4)).
  • the HCl partial pressure is represented by curve C.
  • Addition of 0.5 mol % TCS lowers the entire HCl partial pressure curve relative to curve B.
  • curve C is below curve A and operating conditions are favorable for minimizing or preventing FeCl 2 formation.
  • Increasing TCS to 1 mol % lowers the partial pressure of HCl even further as demonstrated by curve D.
  • a lesser amount of H 2 may be added to the STC process stream when TCS is present.
  • TCS may be obtained by recycling a portion of the product exiting the hydrogenation reactor 30 . However, recycling TCS will at least slightly reduce the yield of the hydrogenation process. Furthermore, if TCS is obtained by recycling, additional energy will be used during the overall process.
  • TCS may be added as a separate component to STC process stream 40 or the combined H 2 /STC feed 42 upstream of the superheater 20 , as shown at 70 in FIG. 1 , or between the superheater 20 and the hydrogenation reactor 30 .
  • TCS can be added to provide a TCS concentration of 0.05 mol % to 2 mol %., such as a concentration of 0.1 mol % to 2 mol %, 0.1 mol % to 1.5 mol %, 0.2 mol % to 1.5 mol %, or 0.5 mol % to 1.5 mol %.
  • the combined H 2 /STC feed may have a hydrogen mole fraction of at least 0.05, particularly a hydrogen mole fraction from 0.05 to 0.9, or 0.1 to 0.7.
  • a desired level of TCS can be maintained in the STC process stream by varying conditions in an STC distillation column 80 such that the STC distillate includes the desired level of TCS.
  • a method for reducing iron silicide and/or iron phosphide fouling and/or corrosion in a hydrochlorosilane production plant comprising a silicon tetrachloride superheater and a hydrogenation reactor includes adding hydrogen to a vaporized silicon tetrachloride process stream upstream of the silicon tetrachloride superheater to form a combined hydrogen/silicon tetrachloride feed having a concentration of hydrogen sufficient to inhibit FeCl 2 vapor formation in the silicon tetrachloride superheater, thereby reducing iron silicide and/or iron phosphide fouling, superheater corrosion, or a combination thereof; flowing the combined hydrogen/silicon tetrachloride feed into the silicon tetrachloride superheater; and subsequently flowing the combined hydrogen/silicon tetrachloride feed into the hydrogenation reactor.
  • the combined hydrogen silicon tetrachloride feed may have a hydrogen mole fraction of at least 0.4
  • hydrogen may be added to the vaporized silicon tetrachloride process stream in an amount sufficient to produce a H 2 /SiCl 4 mole ratio of at least 0.67:1 in the combined hydrogen/silicon tetrachloride feed.
  • the H 2 /SiCl 4 mole ratio is from 0.67:1 to 5:1. In another embodiment, the H 2 /SiCl 4 mole ratio is 1:1.
  • hydrogen may be added to the silicon tetrachloride process stream in an amount sufficient to inhibit superheater corrosion. In any or all of the above embodiments, hydrogen may be added to the silicon tetrachloride process stream in an amount sufficient to inhibit iron silicide fouling, iron phosphide fouling, or a combination thereof in the hydrogenation reactor.
  • the method may further include adding trichlorosilane to the silicon tetrachloride process stream before flowing the combined hydrogen/silicon tetrachloride feed into the silicon tetrachloride superheater.
  • the trichlorosilane is added to the silicon tetrachloride process stream after the hydrogen has been added.
  • trichlorosilane may be added to the combined hydrogen/silicon tetrachloride feed in an amount sufficient to provide a trichlorosilane concentration of 0.05 mol % to 2 mol %, such as 0.5 mol % to 1.5 mol %.
  • the combined hydrogen/silicon tetrachloride feed may have a hydrogen mole fraction of at least 0.05.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
US14/243,822 2013-04-19 2014-04-02 Corrosion and fouling reduction in hydrochlorosilane production Abandoned US20140314655A1 (en)

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JP (1) JP2016521241A (zh)
KR (1) KR20150143794A (zh)
CN (1) CN104470851B (zh)
DE (1) DE112014002024T5 (zh)
TW (1) TWI648219B (zh)
WO (1) WO2014172102A1 (zh)

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CN109963645B (zh) * 2016-11-23 2022-03-11 瓦克化学股份公司 用于氢化四氯化硅的方法

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US20040131528A1 (en) * 2001-06-08 2004-07-08 Kendig James Edward Process for preparation of polycrystalline silicon

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BE792542A (fr) * 1971-12-11 1973-03-30 Degussa Procede pour la fabrication de chlorosilanes exempts de metaux lors de la chloration ou l'hydrochloration de ferrosilicium
US4676967A (en) * 1978-08-23 1987-06-30 Union Carbide Corporation High purity silane and silicon production
US4321246A (en) * 1980-05-09 1982-03-23 Motorola, Inc. Polycrystalline silicon production
JP4813545B2 (ja) * 2005-03-09 2011-11-09 アールイーシー シリコン インコーポレイテッド ヒドロクロロシランの製造方法
US8178051B2 (en) * 2008-11-05 2012-05-15 Stephen Michael Lord Apparatus and process for hydrogenation of a silicon tetrahalide and silicon to the trihalosilane
US8298490B2 (en) * 2009-11-06 2012-10-30 Gtat Corporation Systems and methods of producing trichlorosilane
CN102327769A (zh) * 2011-06-13 2012-01-25 大连理工大学 一种甲烷化催化剂及其应用

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040131528A1 (en) * 2001-06-08 2004-07-08 Kendig James Edward Process for preparation of polycrystalline silicon

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CN104470851B (zh) 2017-06-06
CN104470851A (zh) 2015-03-25
JP2016521241A (ja) 2016-07-21
DE112014002024T5 (de) 2016-01-14
KR20150143794A (ko) 2015-12-23
TW201444769A (zh) 2014-12-01
TWI648219B (zh) 2019-01-21

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